Cobaltiferous monoazo-dyestuffs



United States Patent 2,727,032 COBALTIFEROUS MONOAZO-DYESTUFFS ArthurBuehler, Rheinfelden, and Christian Zickendraht, Binningen, Switzerland,assignors to Ciba Limited, Basel, Switzerland, a Swiss firm No Drawing.Application August 4, 1952, Serial No. 302,626

Claims priority, application Switzerland August 7, 1951 17 Claims. (Cl.260-147) According to this invention .valuable new cobaltiferousazo-dyestutfs are made by treating a monoazo-dyestufi free from sulfonicacid and carboxylic acid groups and corresponding to the general formulain which R1 represents a benzene radical bound to the azo linkage inortho-position relatively to the hydroxyl group, and R2 represents theradical of a coupling component containing an aromatic radical andcapable of coupling in a position vicinal to a hydroxyl group, and inwhich one of the radicals R1 and R2 contains an aromatically boundmethyl sulfone group with an agent yielding cobalt in such manner thatthe resulting cobaltiferous dyestuff contains less than one atom ofcobalt in complex union per molecule of monoazo-dyestuff.

The monoazo-dystufis corresponding to the above general formula andserving as starting materials in the present process can be made fromdiazoand couplingcomponents which are free from sulfonic acid andcarboxylic acid groups and contain an aromatically bound methyl-sulfonegroup, which may be present in the coupling-component or in thediazo-component, but advantageously in the latter component. Suchdyestutt components containing an aromatically bound methyl sulfonegroup are obtained by methods in themselves known by methylating theappropriate sulfinic acids, for example, with dimethylsulfate, or byoxidizing the appropriate aromatic methyl thioethers. 'Thus, themethyl-sulfonylorthoaminophenols valuable in the present process areobtainable from ortho-nitro-chlorobenzene sulfonic acid chlorides byfirst converting the latter by mild reduction with sodium sulfite intothe corresponding sulfinic acids, methylating the latter, then replacingthechlorine atom by a hydroxyl group by means of caustic alkali, andconverting the nitro group into an amino group, for example, byreduction with sodium sulfide.

As examples of diazo compounds coming into consideration there may bementioned those obtained by diazotizing the following amines: H p

(a) Amines containing methyl sulfone groups such as 6-nitroor6-chloro-2-amino-1hydroxybenzene-4-methyl sulfone, 4-nitroor 4-chloro2-amino-l-hydroxybenzeneor 6-methyl sulfone,2-arnino-l-hydroxybenzene-4:6- di-(methyl sulfone) and {especiallyZ-amino-I-hydroxybenzene-4- or 5-methyl sulfone, and also ([2) Compoundscontaining no methyl sulfone groups, (which are therefore coupled onlywith azo components containing methyl sulfone groups), such as 4-nitro-,4-chloro-, 4-methoxyor 4-methyl-2-amino-1-hydroxybenzene,4:6-dichloro-2-amino-l-hydroxybenzene, S-nitro- 2amino-l-hydroxybenzene, 4-nitro-6-ch1oro-2-amino-1- hydroxybenzene,3:4:'6-tricl1loro-2-aminol-hydroxybenzene,3-amino-4-hydroxy-acetophenone, 4-nitro-6-acetylaminoZ-amino-l-hydroxybenzene, 6-nitro-4-acetylamino-Z-amino-l-hydroxybenzene, 4-chloro-2-amino-1-hydroxybenzene5-'- or6-sulfonic acid amide, 6-nitro2-amino-1- hydroxybenzenei-sulfonic acidamide, 2-amino-1-hydroxybenzene-4- or 5-sulfonic acid amide and thecorresponding substituted sulfonic acid amides such as 2-amino-1hydroxybenzene-4-sulfonic acid methylamide, ethylamide, n-butylamide,dimethylamide, diethylamide or phenylamide.

As coupling components to be used for preparing the monoazo-dyestuifsserving as starting materials in the present process, there come intoconsideration those which contain an aromatic radical and owe theircoupling capacity to a phenolic hydroxy group or a keto methylene group.Coupling compounds which are free from methylsulfone groups or whichcontain up to 2 methylsulfone groups may be used. Among the couplingcomponents free from methyl sulfone groups, which are to be coupled onlywith the diazo compounds of the hydroxy-amines mentioned above under(a), there may be mentioned, for example, hydroxyquinolines; phenolssuch as para-cresol or resorcinol; naphthols such as4-methyl-1-hydroxynaphthalene, S-chloroor 5:S-dichloro-l-hydroxynaphthalene, Z-hydroxy-uaphthalene, 6-methoxyor6-bromo-2- hydroxynaphthalene, 1-acetyl-, l-n-butyrylor l-benzoylamino-7- hydroxynaphthalene, Z-hydroxynaphthalene-fisulfonic acid amide orthe corresponding N-methylamide or N-phenylamide; acylacetic acidarylamides, such as acetoacetic acid phenylamide, aceto acetic acidorthochloranilide, l-acetoacetylaminobenzene-3- or 4-sulfonic acidamide; pyrazolones such as 5-pyrazolone-3-carboxylic acid anilide,l-phenyl 3 methyl 5 pyrazolone, 1phenyl-3methyl-S-pyrazolone-3- or4'-sulfonic acid amide, 1phenyl-3-methyl-S-pyrazolone-4-sulfonic acid-N-methylamide, or N-phenylamide, l-phenyl-S-pyrazolone-3-carboxylic acidamide, i-phenyl-S-pyrazolone-B- carboxylic acid-N-butylamide orN-phenylamide, and also 1-(2'- or 3'- or4'-chlorophenyl)3-methyl-5-pyrazolone. Coupling components containingmethyl sulfone groups, which can be coupled either with the diazocompounds obtained from the hydroxy amines mentioned under (a) above orthose mentioned under (b) above, are obtainable, for example, fromaminobenzene methyl sulfones by condensing the latter with diketene orB-ketocarboxylic acid esters to form the corresponding aceto oracylacetic acid anilides, or by converting the amino, group of theaminobenzene methyl sulfones by methods in themselves known into ahydrazine group, and condensing the resulting products withfi-keto-carboxylic acid esters to form l-aryl-S-pyrazolones. It is alsopossible to convert O-acyl-sulfonyl compounds of naphthol sulfonic acidsinto the corresponding sulfonic acid chlorides and sulfinic acids, thento methylate the latter and finally to hydrolyze the O-acyl groups,Especially suitable coupling components of this kind arel-hydroxynaphthalene-3- or 4- or 5-methyl sulfone,Z-hydroxy-napthalene-4- or 6- or 7-methyl sulfone, 1-phenyl-3-methyl-5-pyrazolone-3'-methyl sulfone, 1-phenyl-3-methyl-5-pyrazolone-4-methylsulfone and l-acetoacetylaminobenzene-3- or 4-methyl sulfone.

The coupling of the diazo compounds to be used with thecoupling-components can be carried out by the usual known methods,advantageously in an alkaline medium, for example, a medium renderedalkaline with an alkali carbonate or an alkali hydroxide. After thecoupling reaction the dyestufis can easily be separated from thecoupling mixture by filtration for the tion, since they are onlyslightly soluble in water. They are advantageously used in the form offilter cakes without intermediate drying. In some cases it is alsopossible to carry out the treatment with the agent yielding cobaltdirectly in the coupling mixture, that is to say, without anyintermediate separation.

The treatment with an agent yielding cobalt is carried out in thepresent process in such manner that a cobaltiferpurpose ofmetallizatreatment with the agent yielding cobalt in a weakly acid toalkaline medium. Accordingly, there are especially suitable for thepresent process those cobalt compounds which are stable in alkalinemedia such, for example, as complex cobalt compounds of aliphaticdicarboxylic acids or hydroxy-carboxylic acids. As examples of aliphaticdicarboxylic acids and hydroxycarboxylic acids there may be mentioned,among others oxalic acid, lactic acid, glycollic acid, citric acid andespecially tartaric acid. As agents yielding cobalt there can also beused with advantage in the present process simple cobalt salts such ascobalt sulfate or cobalt acetate, and also cobalt hydroxide.

The conversion of the dyestuffs into the complex cobalt compounds isadvantageously carried out with the aid of heat, under atmospheric orsuperatmospheric pressure,

and if desired in the presence of suitable additions, for example, inthe presence of salts of organic acids, bases, or organic solvents orother agents assisting the formation of complexes.

In a special form of the process there is used as starting material amixture of difierent metallizable monoazodyestuifs, each of whichcorresponds to the general definition given above. The treatment withthe agent yielding cobalt is carried out in this case also in suchmanner that the resulting cobaltiferous dyestuffs contain less than oneatom of cobalt in complex union per molecule of monoazodyestuff;

The new cobaltiferous dyestuffs of this invention are cobalt compounds,containing less than one atom of cobalt bound in complex union permolecule of dyestuff, and advantageously one atom of cobalt bound incomplex union to substantially two molecules of monoazo-dyestuifs freefrom sulfonic and carboxylic acid groups and corresponding to thegeneral formula (1)11 Ri- -N-Rz in which R1 represents a benzene radicalbound to the azo linkage in ortho-position relatively to the hydroxylgroup, and R2 represents the radical of a coupling component capable ofcoupling in a position vicinal to a hydroxyl group and which couplingcomponent contains an aromatic radical, and in which one of the radicalsR1 and R2 contains an aromatically bound methyl sulfone, group.

These complex cobalt compounds are soluble in water and in weakly acidaqueous media and are indeed more soluble than the dyestuffs used formaking them. They are suitable for dyeing or printing a very widevariety of materials, above all for dyeing animal materials, such assilk, leather and especially wool, but also for dyeing or printingsynthetic fibers of superpolyamides or superpolyurethanes. They aresuitable above all for dyeing from weakly alkaline or neutral to weaklyacid, for example, acetic acid, baths. The wool dyeings so produced aredis tinguished by their level character and good properties of wetfastness, good fastness to decatizing and carbonizing and very goodfastness to light.

The following examples illustrate the invention, the parts andpercentages being by weight:

Example 1 18.7 parts of Z-amino-lhydroxybenzene-4-methylsulfone aredissolved in 100 parts of water and 23.4 parts of hydrochloric acid of30 per cent. strength, and diazotized at -5 C. by means of an aqueoussolution of 6.9 parts of sodium nitrite. The diazo suspension isneutralized with sodium carbonate, and poured at 10l2 C.

into a solution of 18 parts of 1-phenyl-3-methyl-5-pyrazolone in 200parts of water and 13.3 parts of sodium hydroxide solution of 30 percent. strength. Coupling proceeds very rapidly. The dyestuif formedprecipitates al- 5 most completely. It is filtered off, stirred with 300parts of water, and dissolved by the addition of 26.6 parts of sodiumhydroxide solution of 30 per cent. strength. The solution is mixed atESQ-85 C. with a solution of 16 parts of crystalline cobalt sulfate(CoSO4.7I-I2O) in 100 parts of water, stirred for 30 minutes at thattemperature, and the whole is then filtered. The filtrate is evaporatedin vacuo. The cobaltiferous dyestufi' so obtained is a water-.

soluble brown powder, which dissolves in concentrated sulfuric acid withan orange-yellow coloration and dyes wool from a neutral or acetic acidbath yellow-brown tints having good properties of fastness.

In the following table are given a few further complex metal compoundswhich can be made by the process of this example. In all cases cobalt isthe metal forming the complex. In column I are given thediazo-components and in column II the coupling components, and in columnIII are given the tints of the dyeings obtainable by dyeing 100 parts ofwool with 2 parts of the cobalt compound from a neutral or acetic acidbath.

I II III 1. 2-Amino-1-hydroxy-ben- Z-hydroxyhaphthalene. reddishborzene-4-methyl sulfone. deaux. 6-bromo-2-hydroxybordeaux.

naphthalene. 5:8-dichloro-1-hydroxybluish bornaphthalene. deaux.aeetoacetylamino-benyellow.

zene. 1-(4-chlorophenyl)-3- brown yelmethyl-5-pyrazolone. low. 6......do l-acetoacetylamino-Z- yellow.

chlorobenzene. I 7... l-acetylamino-7-hygreyish viodroxynaphthalene.let. 8. l-phenyl-S-methyl-S-pyb r 0 w n or razolone-lniethylstilange.toner 9. 1-pheny1-3-methyl5-pyb r o w n i s h tazolone-3-suli0nicyellow.

acid amide.v

10. Z-amino-l-hydroxy-ben- 1-pl1enyl-3- ethyl-fi-pyorange.

zene-5-methyl sulfone. razolone.

11.. acetoacetylamino-benreddish yelzene. low.

12- .---do B-naphthol bordeaux.

13- 2-amino-1-hydroxy-ben- Z-hydroxynaphthalene- Do.

zene-i-sulfonic acid 7-methyl sulfone. methylamide.

14- Z-amino-l-hydroxy-ben- 5:8-dichloro-1-hydroxyviolet.

zene-5-methyl-sulfone. naphthalene.

15.. do l-(4-ehlorophenyl)-3- orange.

methyl-5-pyrazolone.

16- 4-nitro-2-amino-1-hy- 1-phenyl-3-methyl-5-pyb r o w n i s hdroxybenzene. razolone-4-methy1- yellow.

snltone.

17.. 5-nitro-2-amino-1-l1y- .---.do r e d d i s h droxybenzene. brown.

18- 4-chloro-2-amino-1-hy- ...do b r o w n i s h droxybenzene. 7 yellow.

19. 2-amino-1-l1ydroxybenl-acetoacetyl-aminoyellow.

zene-t-sulfonic acid benzene-i-rnethyl sulamide. tone.

20. 2-amino-l-hydroxy-ben- -....do b r o w n i s h zenet-sultonic acidyellow. anilide.

21 3-amino-4-hydroxy-ace- ..do Do.

tophenone.

22. 4-nitro-2-amino-1-hy- ..-do Do.

droxybenzene.

Example 2 19.95 parts of the dyestuff obtained from diazotized 2-amino-l-hydroxybenzene-4-methyl sulfone and l-acetyl- Iamino-7-hydroxynaphthalene, and 20.3 parts of-the dyestnfl? obtainedfrom diazotized z-amino-l-hydr'oxybenzene- 4-methyl sulfone andl-(4'-chlorophenyl)-3-methy1-5- pyrazolone are dissolved together in2000 parts of water with the addition of 8 parts of sodium hydroxide,and mixed at 80 C. with 100 parts of a cobalt sulfate solution having acobalt content of 3.25 per cent. After stirring for about /2 hour at 80C. the metallization is finished. The cobalt complex is precipitated bythe addition of sodium chloride. When dry it is a brown powder whichdissolves in water with a brown coloration and in concentrated sulfuricacid with an orange coloration, and dyes wool from a weakly alkalinebath or a neutral or acid bath full brown tints having an excellentfastness to washing, decatizing and carbonizing.

Dyestufis having similar properties are obtained by using instead of themonoazo-dyestuffs mentioned in the preceding paragraph the dyestuffsgiven in the following table, and otherwise proceeding in an analogousmanner. In columns A and B are given the twoortho:ortho'-dihydroxymonoazo-dyestufls bound in complex union tocobalt, and in column C are given the tints obtained by dyeing wool froman acetic acid or neutral bath.

A B C 1 2-Amino-l-hydroxy-b en- Z-amino-I-hydroxy-benbordeaux.

zene 4 methylsulfone zene 4 methylsulfone 2-hydroxynaphtha- 5:8-dichloro l-hylene. droxynaphthalene. 2 2-amino-l-hydroxy-bendoreddish zene 4 methylsultone brown.

- 1 acetoacetylami no-2-chlorobenzene. 3-.." 4 -nitro 2- amino 1 -hy-2-amino -1 -hydroxybenbrownish droxybenzene 1 zene 4 methylsulfoneyellow.

phenyl 3 methyl 5 l acetoacetylamr pyrazolone 4 methylno-2-chlorobenzene.

one.

Example 3 0.5 part of the cobaltiferous dyestuif obtained as describedin Example 1 is dissolved in 4000 parts of water, 10 parts ofcrystalline sodium sulfate are added, and 100 parts of well wetted woolare entered at 40-50 C. into the resulting dyebath. 3 parts of aceticacid of 40 per cent. strength are then added, the bath is raised to theboil in the course of /2 hour, and dyeing is carried on for /1 hour atthe boil. Finally the wool is rinsed with cold Water and dried. There isobtained a level brownjyellow dyeing having good properties of fastnessto washing and light.

Practically the same dyeing is obtained if no acetic acid is added tothe dyebath.

What is claimed is:

1. A complex cobalt compound containing one atom of cobalt bound incomplex union with substantially to monoazo dyestufis free from sulfonicacid and carboxylic acid groups, which correspond to the formula Il1N=NRz wherein R1 represents a benzene radical bound to the azo-linkagein ortho-position relatively to the hydroxyl group, and R2 represents aradical selected from the group consisting of a hydroxynaphthaleneradical bound to the azo-linkage in a position vicinal to the hydroxygroup, a l-phenyl-S-pyrazolone radical bound to the azo-linkage in4-position, and the radical of a B-ketocarboxylic acid arylide bound tothe azo-linkage in a-position, and wherein at least one of the radicalsR1 and R2 contains an aromatically bound methyl sulfone group.

2. A complex cobalt compound containing one atom of cobalt bound incomplex union to substantially two molecules of a monoazo dyestufl freefrom sulfonic acid and carboxylic acid groups, which corresponds to theformula wherein R1 represents a benzene radical bound to the a'zolinkagein ortho-position relatively to the hydroxyl group, and R2 represents aradical selected from the group consisting of a hydroxynaphthaleneradical bound to the azo linkage in a position vicinal to the hydroxygroup, a l-phenyl-5-pyrazolone radical bound to the azo-linkage in4-position, and the radical of a ,B-ketocarboxylic acid arylide bound tothe azo linkage in a-position.

3. A complex cobalt compound containing one atom of cobalt bound incomplex union to substantially two molecules of a monoazo dycstufi freefrom sulfonic acid and carboxylic acid groups, which corresponds to theformula 0 O-CH:

SOICHS wherein R1 represents a benzene radical bound to the azo linkagein ortho-position relatively to the hydroxyl group.

4. A complex cobalt compound containing one atom of cobalt bound incomplex union to substantially two molecules of a monoazo dyestuff freefrom sulfonic acid and carboxylic acid groups, which corresponds to theformula COOH:

wherein X represents a member selected from the group consisting of anitro group, a chlorine atom, a sulfonic acid amide group, and a COCH3group.

5. A complex cobalt compound containing one atom of cobalt bound incomplex union to substantially two molecules of a monoazo dyestufi freefrom sulfonic acid and carboxylic acid groups, which corresponds to theformula SOa-CHs wherein R2 represents a 2-hydroxynaphthalene radicalbound to the azo-linkage in l-position.

6. A complex cobalt compound containing one atom of cobalt bound incomplex union to substantially two molecules of a monoazo dyestufi freefrom sulfonic acid and carboxylic acid groups, which corresponds to thewherein R3 represents a benzene radical.

7. A complex cobalt compound containing one atom of cobalt bound incomplex union to substantially two molecules of a monoazo dyestufi freefrom sulfonic acid and carboxylic acid groups, which corresponds to theformula 8 :03: wherein R3 represents a benzene radical.

8. A complex cobalt compound containing one atom of cobalt bound incomplex union to substantially two molecules of a monoazo dyestuficorresponding to the formula I COCH:

SOzOHS 9. A complex cobalt compound containing one atom of cobalt boundin complex union to substantially two molecules of a monoazo dyestuft'corresponding to the formula OH HO I -Q N=N-O l S 2C Ha iu. A complexcobalt compound containing one atom of cobalt bound in complex union tosubstantially two molecules of a monoazo dyestuff corresponding to theformula OH H I I S 62 C Ha X wherein X represents a member selected fromthe group consisting of a hydrogen and a bromine atom, and Y representsa member selected from the group consisting of an 'acetylamino group anda hydrogen atom, at least one of the two symbols X and Y standing forhydrogen.

11. A complex cobalt compound containing one atom of cobalt bound incomplex union to substantially two 7 molecules of a monoazo dyestuficorresponding to the molecules of a monoazo dyestufi corresponding tothe formula COCHa l SO2CH3 00011:

13. The complex cobalt compound containing one atom of cobalt bound incomplex union to substantially two molecules of the monoazo dyestufi ofthe formula 14'. The complex cobalt compound containing one atom ofcobalt bound in complex union to substantially two molecules of themonoazo dyestufi of the formula OH 7 HO (I11 m SOaCHa C1 15. The complexcobalt compound containing one atom of cobalt bound in complex union tosubstantially two molecules of the monoazo dyestulf of the formula OHHCI) SOzCH:

16. The complex cobalt compound containing one atom of cobalt bound incomplex union tosubstantially two molecules of the monoazo dyestufi ofthe formula OH 3T0 I SOzCHs 17. The complex cobalt compound containingone atom of cobalt bound in complex union to substantially two moleculesof the monoazo dyestuff of the formula OzCHa References Cited in thefile of this patent UNITED STATES PATENTS Felix et a1. Dec. 9, 1947Schetty May 1, 1951

1. A COMPLEX COBALT COMPOUND CONTAINING ONE ATOM OF COBALT BOUND INCOMPLEX UNION WITH SUBSTANTIALLY TO MONOAZO DYESTUFFS FREE FROM SULFONICACID AND CARBOXYLIC ACID GROUPS, WHICH CORRESPOND TO THE FORMULA